Production of valuable organic oxygen compounds



Patented Apr. 21, 1931 UNITED STATES HEINRICH HOIIF, OI" LUDWIGSHAIEN-ON-THE-RHINE, GERMANY, ASSIGNOB TO I.

IARBENINDUSTRIE AKTIENGESELLSCHAIT, F FRANKFORT-ON-THE-MAIN', GEE- MANY, A. CORPORATION OF GERMANY 7 PRODUCTION OF VALUABLE ORGANIC OXYGEN GOMPOUl-TDS Ho Drawing. Application filed September 12, 1928, Serial No. 305,816, and in Germany November 5, 182?.

This invention relates to the'pr'oduction of valuable organic compounds.

I have found that valuable oxygen compounds can be produced from non-aromatic hydrocarbons e. g. from aliphatic or hydro-- aromatic hydrocarbons, or mixtures thereof by the action thereon of carbon monoxid under pressure, in the presence of anhydrous halides of aluminium or boron or-mixtures 10 thereof, the pressure being variable within wide limits. A suitable working pressure is from about 80 to 150 atmospheres, though it will be understood that lower and any attainable higher-pressures may be employed. The reaction proceeds, though slowly even in the cold and at rather low pressure such as about 50 atmospheres but it is preferable to work at an elevated temperature and at a pressure above the aforesaid pressure though, when heating, a pressure of about 10 atmospheres only can be applied.

Both individual hydrocarbons, and the cheaper mixtures of hydrocarbons, such as occur in the various petroleum fractions and are practically free from aromatic hydrocarbons, as for example petroleum ether, ligroin, lamp oil and purified petroleum elly, also brown coal tar oils, the products of a destructive hydrogenation of substances of the nature of coal, tar, mineral oils and the like, cracking products and similar substances may be treated in this manner.

In the abovereaotion besides aluminium chlorid, anhydrous aluminium bromid, b0- ron fluorid and the like may be employed.-

The following examples will further illustrate the nature of the said invention which however is not limited thereto. The parts are by weight; 4

Example 1 A high pressure retort fitted with stirrers is charged with 100 parts of normal pentane and 100 parts of anhydrous aluminium chlorid. Air is expelled from the vessel by curs.

repeated admission of carbon monoxid under pressure, whereupon carbon monoxid is admitted under a pressure of from about 126 to 150 atmospheres, and the retort is heated to a temperature of about between 35 and 60? 0., the stirrers being set in motion. A sorption of carbon monoxid begins after a short time and the pressure drops to from to atmospheres in the course of 5 8 hours. More carbon monoxid is then forced in until a. pressure of to atmospheres is again attained, stirring being continued, and the admission of carbon monoxid is repeated until no further drop in pressure oc- The reaction product consists of two liquid layers. The upper is composed or unaltered pentane and is removed. The dense, viscous lower layer is a double compoundof aluminium chlorid and the reaction product. It is poured onto ice, acidified with hydrochloric acid and distilled in a current of steam. The major portion passes over with the steam and is contained in the distillate as an oily layer. After separating the oil from the water, shaking it with dilute caustlc soda-solution and separating again, 1t 1s fractionated by distillation. A considerable portion thereof boils between 114- and 116 C. and is obtained as a colorless liquid having a strong odour. The analysis of the product gives values corresponding to the formula O H O; the product is identical with ethyl isopropyl ketone. The main fraction boils between 116 and 250 C. and consists of a mixture of higher ketones which have probably been produced by condensation of the above mentioned simple ketone under the influence of the aluminium chlorid. The said higher ketones consist of colourless oils having a pleasant odour similar to that of menthol. From the caustic soda solution an oil with a rancid odour'can be recovered by acidification, which oil boils between and 300 C. and consists-for the tort is heated u main portion of a carboxylic acid corre- Ezample 2 A high (pressure retort fitted with stirrers is charge with 100 parts of cyclo-hexane and parts of anhydrous aluminium chlorid. Air is'expelled from the vessel by repeated admission of carbon. monoxid under pressure, followed by release of the ressure, whereupon carbon monoxid is a mitted undera pressure of about 120 atmospheres and the reto about C. The reaction soon be 1118, the tem erature rising somewhat, an the pressure ro s rapidly to about20 atmospheres. More car on monoxid is then forced in until a pressure of 120 atmospheres is attained and the admission'of carbon monoxid isrepeated until no further dro in pressure occurs.

e reaction product consists of two layers, the 11 per of which is composed of unchanged cyclo exane and is separated off. 'The darkbrown colored lower layer is a double compound ofaluminium chlorid and the reaction product. It is poured onto ice; acidified with V ydrochloric acid and subjected to steam distillation. The major portion passes over with the steam and is contained in the distillate as an oily layer. After being separated from the water, the said oil is fractionated by distillation in vacuo. The reaction pro duct distills over in an almost quantitative amount at between and 150 C- at a pressure of 12 millimeters. The distillate consists of a slightly colored oil, which has an agreeable odour and an oxygen content of about 12 r cent.

That portion of the reaction product which is not 'volatili'zed with steam consists of a dark-colored, highly viscous oil.

In place of c clohexane, other hydroaromatic hydrocar ons such as hexahydro toluene, or mixtures of hydroaromatic hydrocarbons from mineral oils, orthe products of the destructive hydrogenation of substances of the nature of coal, tar, mineral oils and the like, lignite tar oils and similar substances may be employed. Example :9

A. mixtureiof 300 parts of n-butane and 300 parts of anhydrous aluminium chlorid is treated with carbon monoxid at 50 C. and

about atmospheres, while stirring in the manner described in Exam le 1 until no fur-' Example 4 500 parts of point offrom 35 to 50 C. are treated together with 500 parts of anhydrous aluminium chlorid with carbon monoxid at 50 C. and about 120 atmospheres while stirring, in the manner described in lixample 1, until no further absorption of carbon monoxid takes" place, and the reaction product is worked up in the manner described. About 300 parts of a colorless oil of agreeable smell is obtained which possesses a similar composition as the product obtained form n-pentane according to Example 1. I

500 parts of a lieavy benzine with a boiling point range from 150 to 200 C. are treated with 300 parts of anhydrous aluminium chlorid and carbon monoxid, the latter being introduced under a pressure of 150 atmospheres and at 50 (1., while stirring. By working u there is obtained about 400 parts of a (la oil of peculiar smell which can be fractionated by distillation, the fractions of lower boiling point possessing a pleasant'aromatic odour.

Example 6 800 parts of a petroleum fraction boiling from 150 to 300 C. which is free from olefines are stirred with 600 parts of anhydrous aluminium chlorid and carbon monoxid at 50 C. under a pressure of 150 atmospheres, carbon monoxid being added untila constant pressure within the reaction vessel is attained. On working u the reaction prodnot, about 600 partso a black oil are obtained from which 30 per cent can be obtained in the form of a pale yellow oil which is volatile with steam and has a pleasant odour. The dark constituents which are not volatile withv steam are viscous and can be employed as a lubricating oil.

What I claim is;-

1. The process for the production of valuable organic oxy compounds which comprises acting wi carbon monoxid and an anhydrous halide of aluminium u 'n a nonaromatic; hydrocarbon in the liquid states at a pressure above 10 atmospheres.

2. The process forthe production of valuable organic oxygen compounds which competroleum ether with a boiling Ill iao

prises acting with carbon monoxid and an anhydrous halide of aluminium upon a mix-' ture of non-aromatic hydrocarbons in the liquid state at a pressure above 10 atmospheres.

3. The process for the production of valuprises acting with carbon monoxid and an anhydrous halide of aluminium upon a nonaromatic hydrocarbon in the liquid state at a pressure above 10 atmospheres while heating to a temperature between room temperature and about 150 C.

6. The process for the production of valuable organic oxygen compounds which comprises acting with carbon monoxid and an anhydrous halide of aluminium upon a mixture of non-aromatic hydrocarbons in the liquid state at a pressure above 50 atmospheres while heating to a temperature between room temperature and about 100 C.

7. The process for the production of valuable organic oxygen compounds which comprises acting with carbon monoxid and anydrous halides of aluminium and of boron upon a fraction of amineral oil in the liquid state at a pressure above 50 atmospheres while heating to a temperature between room temperature and about 100 C. Y

8. The process for the production of valua b1e organic oxygen compounds which comprises acting with carbon monoxid and anhydrous aluminium chlorid upon a non-' aromatic hydrocarbon in the liquid state at a pressure between 10 and 150 atmospheres while heating to a temperature between room temperature and about 150 C.

9. The process for the production of valuableo'rganic oxygen compounds which comprises acting with carbon monoxid and anhydrcus aluminium chlorid upon a mixture of non-aromatic hydrocarbons in the liquid state -at a pressure between 80 and 150 atmos- Eireres while heating to a temperature tween room temperature and about 100 C.

10 The process for the production of valuable organic oxygen compounds which comprises acting with carbon monoxid and anhydrous aluminiumchlorid upon a fraction of a mineral oil in the liquid state at a pressure between. 80 and 150 atmospheres room temperature and about 100 C.

11. The process for the production of valuable organic oxygen compounds which comprises acting with carbon monoxid and anhydrous aluminium chlorid upon petroleum ether at a pressure between 80 and 150 atmospheres while heating to a temperature between room temperature and about 60 C.

a In testimony whereof I have hereunto set my hand.

HEINRICH HOPFF. 

